JPH0543831A - Coating resin and coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating resin which is excellent in compatibility with curing agents and capability of dispersing pigments and also gives films excellent in weather resistance and resistance to stains, and a coating composition prepared therefrom. CONSTITUTION:A coating resin comprising primary a resin (A) with a number- average molecular weight of 500-50,000 which contains fluorine and also active hydrogen and/or epoxy groups in the molecule and an acrylic resin (B) with a number-average molecular weight of 500-50,000 which has a UV absorbing capacity and/or an oxidation preventive capacity and/or a capacity as radical scavenger in the molecule in a weight ratio of the resins (A) to (B) of 95:5 to 5:95. A coating composition formed by mixing the resin with a curing agent. A process for producing the coating resin by polymerizing a monomer for forming the resin (A) in the presence of the resin (B), or by polymerizing a monomer for forming the resin (B) in the presence of the resin(A).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a weather resistant coating resin, a method for producing the same, and a coating composition.

[0002]

2. Description of the Related Art A resin for a fluorine-containing coating composition, which uses polyisocyanate compounds or melamine compounds as a curing agent and is crosslinked and cured at room temperature or under heating and exhibits excellent weather resistance, is disclosed in, for example, JP-A-57-34107. Japanese Patent Publication No. Sho 58
No. 34866, No. 59-102962, No. 61-275311, and No. 62-2.
It is known from Japanese Patent No. 88666.

However, these fluorine-containing coating resins generally have a little compatibility with curing agents, especially polyisocyanate type curing agents having excellent room temperature curing properties, dispersibility of pigments, stain resistance of cured coating films and the like. It is said to have weaknesses.
In order to overcome these drawbacks, for example, JP-A-55-2
As is seen in Japanese Patent No. 5419 and Japanese Patent Laid-Open No. 61-12760, it has been proposed to use a resin for fluorine-containing coating and an acrylic resin in a blend.

However, although such a weakness is compensated for in such a blend system, it has a major drawback that the essential weather resistance is lower than that of a system containing a fluorine-containing coating resin alone. Further, for example, JP-A-61-2740, JP-A-62-141048 and the like propose adding a compound having an ultraviolet absorbing ability and a radical scavenging ability to a resin for a fluorine-containing coating material. However, since all of these additives have small molecular weights, they have the drawback of bleeding out of the coating film after long-term exposure.

[0005]

That is, an object of the present invention is to provide a coating resin excellent in compatibility with a curing agent, dispersibility of a pigment, stain resistance and the like, and also excellent in weather resistance. is there.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in view of the above points, and as a result, by using a resin for fluorine-containing coating and a resin having a specific functional group together, the above problems can be solved. They found that they could be solved, and completed the present invention.

That is, the present invention is: number-average molecular weight of 500 to 50,0 containing fluorine in the molecule and having active hydrogen and / or epoxy group.
No. 00 resin (A) and an acrylic resin (B) having a number average molecular weight of 500 to 50,000 and having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule. And a weight ratio of the resin (A) to the resin (B) is 95: 5 to 5:95, and relates to a coating resin,

[0008] In the presence of an acrylic resin having a number average molecular weight of 500 to 50,000 having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule, fluorine is contained in the molecule, and The present invention relates to a method for producing a resin for paints, which comprises polymerizing a monomer that constitutes a resin having active hydrogen and / or an epoxy group,

Number average molecular weight 50 containing fluorine in the molecule and having active hydrogen and / or epoxy group
In the presence of a resin of 0 to 50,000, a monomer constituting an acrylic resin having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in a molecule is polymerized. , A method for producing a resin for paint, and further

Number average molecular weight 50 containing fluorine in the molecule and having active hydrogen and / or epoxy group
Mainly a resin (A) having a number average molecular weight of 500 to 50,000 having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in a molecule. It is used as a component, and the curing agent (II) is mixed with the coating resin (I), which is characterized in that the weight ratio of the resin (A) and the resin (B) is 95: 5 to 5:95. The present invention relates to a coating composition.

The resin (A) containing fluorine in the molecule and having active hydrogen and / or epoxy group used in the present invention includes, for example, (a) JP-A-57-34107 and JP-A-58. -1
36662, JP-A-62-288666,
JP-A-63-110265, JP-A-59-219
372, JP 59-102962, JP 61-113607, and JP 61-27531.
No. 1, JP-A-62-169810, JP-A-Sho 6
1-57609, JP-A-63-182312, JP-A-59-102961, JP-A-63-8.
3108, JP-A-63-218715, JP-A-63-213508, JP-A-64-6061.
No. 6, JP-A-61-141713, etc.,

For example, at least one fluorine-containing olefinic monomer represented by vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, hexafluoro-methyl vinyl ether, etc., A copolymer with a monomer component capable of introducing a hydroxyl group and / or an epoxy group into a copolymer capable of being copolymerized therewith, and a copolymer with any other monomer component.

(B) For example, JP-A-58-34866, JP-A-59-145274, and JP-A-63-1.
As described in JP-A-05015, it is possible to introduce a hydroxyl group and / or an epoxy group into at least one (meth) acrylate-based copolymer having a fluoroalkyl group in its side chain and a copolymer copolymerizable therewith. Copolymer with a monomer component and any other monomer component. Etc.

Among them, the copolymer represented by the above (a) is preferable, and as the more preferable copolymer (a), a fluoroolefin represented by the following general formula (I) is used as a fluorine-containing olefin monomer. What was

[0015]

[Chemical 1] (X and Y may be the same or different, and F and C respectively.
1 or H) is particularly preferable.
At least one selected from chlorotrifluoroethylene, hexafluoropropene, and tetrafluoroethylene is used.

In this case, examples of the copolymerizable monomer component capable of introducing active hydrogen include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and 4-hydroxycyclohexyl vinyl ether; 2-hydroxyallyl vinyl ether. , Hydroxyalkyl allyl ethers such as 4-hydroxybutyl allyl ether; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxypropyl (meth) acrylate; 2-hydroxyethyl crotonate, 4 Typical examples include hydroxy group-containing crotonic acid esters such as hydroxypropyl crotonate; and allyl alcohol.

Of these, hydroxyalkyl vinyl ethers are preferred because of their good reactivity with fluoroolefins. Further, examples of the copolymerizable monomer component capable of introducing an epoxy group include glycidyl vinyl ether, glycidyl allyl ether, and glycidyl (meth) acrylate.

Other monomer components include, for example, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, neopentyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, pentafluoroethyl vinyl ether, 2-perfluoro. Vinyl ethers such as octyl ethyl vinyl ether; alkyl allyl ethers such as ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, 2-ethylhexyl allyl ether; vinyl acetate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl pivalate, versatile Vinyl acetate, vinyl benzoate, pt-
Carboxylic acid vinyl esters such as vinyl butyl benzoate and vinyl laurate; alkyl allyl esters such as allyl acetate, allyl butyrate, allyl 2-ethylhexanoate, allyl benzoate, allyl cyclohexanecarboxylate, allyl cyclohexylpropionate: and Various acrylic acid and methacrylic acid esters; Fumaric acid esters;
Representative examples include maleic acid esters; crotonic acid esters; various unsaturated hydrocarbons.

Further, as shown in Japanese Patent Application No. 1-237122, a fluorine-containing copolymer having a cyclic hydrocarbon group introduced via a urethane bond, and Japanese Patent Application No. 2-1016.
95, a fluorine-containing copolymer containing an endocyclic vinyl ether can also be preferably used.

The resin (A) containing fluorine in the molecule and having active hydrogen and / or an epoxy group used in the present invention is a vinyl monomer having a predetermined ratio in the presence or absence of a solvent. The body mixture can be produced by copolymerization using a polymerization initiator, ionizing radiation or the like as a polymerization initiation source.

As the polymerization initiator, a water-soluble one or an oil-soluble one is appropriately used depending on the type of polymerization or desired.

The polymerization method is not particularly limited, and for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like can be used. From the viewpoint of stability of the polymerization reaction operation, etc. Lower alkyl-substituted benzenes such as xylene and toluene; esters such as butyl acetate; ketones such as methyl isobutyl ketone; alcohols such as t-butanol; saturated halogenated hydrocarbons having at least one fluorine atom as a solvent. The solution polymerization method, the emulsion polymerization method in an aqueous medium, and the bulk polymerization method that does not require separation from the solvent are preferably used.

Further, the polymerization system is not particularly limited, and any of batch system, semi-continuous system and continuous system can be used.

The resin (A) containing fluorine in the molecule and having active hydrogen and / or an epoxy group used in the present invention has a molecular weight of tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight is used as a standard substance. ,
The number average molecular weight (Mn) determined by gel permeation chromatography (GPC) method is 500 to 5
10,000, preferably in the range of 2,000 to 30,000, and the glass transition temperature (Tg) is usually -50 to 12.
It is 0 ° C., preferably −20 to 90 ° C.

When the molecular weight is lower than the above range,
When it is used as a main agent for paints, the strength, hardness, weather resistance and the like of the coating film become defective, and when it is too high, the viscosity of the resin becomes too high and handling becomes difficult, which is not preferable. The content of active hydrogen and / or epoxy group is 3 to 50 mol%, preferably 5 to 30 mol%.

The acrylic resin (B) containing a functional group having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule used in the present invention is described in JP-A-1-261409. Japanese Patent Laid-Open No. 1-28
As seen in 2270 publication,

[0027]

[Chemical 2] (In the formula, R _{1 to} R ₄ each independently have 1 to 18 carbon atoms.
Represents an alkyl group of R ₅ is hydrogen or has 1 to 18 carbon atoms.
Represents an alkyl group. ) Having a so-called hindered amine-based functional group, for example,

[0028]

[Chemical 3] What has what is called a hindered phenol type functional group, Furthermore, what has a benzophenone type functional group, a benzotriazole type functional group, etc. are illustrated, for example.

In order to introduce the functional group having the ultraviolet absorbing ability and / or the antioxidant ability and / or the radical scavenging ability into the resin, (meth) acrylic ester, (meth) acrylamide, vinyl ether of these functional groups are introduced. ,
Generally, a copolymerization reaction between a polymerizable monomer derivative such as vinyl ester and allyl ether and a copolymerizable monomer containing other (meth) acrylic ester as an essential component is used. It is also possible to introduce it into the side chain of the acrylic resin by post-reaction.

The amount of the functional group having the ultraviolet absorbing ability and / or the antioxidant ability and / or the radical scavenging ability in the resin (B) is 0.01 to 40% by weight, preferably 0.1 to 20% by weight. A weight% range is preferred.

Further, like the resin (A), the resin (B) preferably contains active hydrogen and / or an epoxy group in the molecule, which is a comonomer component, for example ( Monomer component having active hydrogen and / or epoxy group such as (meth) acrylic acid, crotonic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 4-hydroxybutyl vinyl ether, glycidyl vinyl ether and glycidyl allyl ether It is achieved by using a part of. In this case, since the resin (B) can also have a crosslinked structure when the resin for coating material containing the resin (A) and the resin (B) as the main components is cured, the physical properties of the resulting coating film are significantly improved.

The resin (B) of the present invention, like the resin (A), uses the above-mentioned vinyl monomer mixture in a predetermined ratio in the presence or absence of a solvent as a polymerization initiator or an ionization initiator. It can be produced by copolymerization using actinic radiation or the like.

The resin (B) thus obtained does not necessarily have to be a fluorinated copolymer, but those containing a fluoroalkyl group in the side chain are not only excellent in compatibility with the resin (A). It is suitable because it remarkably improves the water and oil repellency. Regarding the content of the fluoroalkyl group that exhibits these effects, the fluorine content must be 0.01% by weight or more, preferably 0.1% by weight or more.

The molecular weight of the resin (B) containing a functional group having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule used in the present invention is
The number average molecular weight (Mn) determined by gel permeation chromatography (GPC) method is 500 to 50,000, preferably 2, using tetrahydrofuran as a solvent and monodisperse polystyrene having a known molecular weight as a standard substance. The glass transition temperature (Tg) is usually from -50 to 120 ° C, preferably-
20 to 90 ° C.

When the molecular weight is lower than the above range,
When it is used as a main agent for paints, the strength, hardness, weather resistance and the like of the coating film become defective, and when it is too high, the viscosity of the resin becomes too high and handling becomes difficult, which is not preferable.

The preferred resin (B) is a hydroxyl group-containing acrylic resin having a number average molecular weight of 2,000 to 30,000 and a resin component hydroxyl value of 25 to 200 having a hindered amine functional group represented by the formula: in the side chain. It is a resin. When such a resin is used as the resin (B) of the present invention,
The coating material containing the resin (A) and the resin (B) as the main components is remarkably excellent in gloss, hardness, pigment dispersibility, weather resistance and the like.

The composition ratio of the resin (A) and the resin (B) is 5:95 to 95: 5, preferably 10:90, in terms of the resin weight ratio.
Is selected from the range of 90:10. When the amount of the resin (A) is less than this range, the chemical resistance and the like are poorly expressed, and when it is too large, it is weak in compatibility with the curing agent, dispersibility of the pigment, stain resistance of the cured coating film, and the like. Appear, which is not preferable.

The resin (A) of the present invention containing fluorine in the molecule and having active hydrogen and / or epoxy group and having a number average molecular weight of 1,000 to 50,000, and an ultraviolet absorbing ability in the molecule, And / or antioxidant ability and / or radical scavenging ability, number average molecular weight 1,000 to 5
It is composed mainly of 50,000 acrylic resin (B), and the weight ratio of resin (A) and resin (B) is 95: 5.
As a method for producing a coating resin, which is characterized by: to 5:95, the following methods (a) to (c) can be mentioned.

(A) The resin (A) and the resin (B) are blended. (B) In the presence of the resin (B), the monomers forming the resin (A) are polymerized. (C) In the presence of the resin (A), the monomers constituting the resin (B) are polymerized. As the method for producing the coating resin (I) of the present invention, the above methods (a) to (c) can be arbitrarily selected,
The method (c) is useful as a method for providing a non-aqueous dispersion of a fluorocopolymer containing the fluororesin (A) as a dispersion stabilizer.

When the resin thus obtained is used as the main component of the coating composition, the following curing agents are usually used. For example, so-called melamine-based curing agents such as hexamethoxymethylol melamine and its condensed polynuclear body, hexabutoxymethylol melamine and its condensed polynuclear body.

For example, hexamethylene diisocyanate (HDI), 3-isocyanatomethyl-3,5,5-
Trimethylcyclohexyl isocyanate (IPD
I), bis (4-isocyanatocyclohexyl) methane (hydrogenated MDI), 1,3- (or1,4-) bis (isocyanatomethyl) benzene (XDI), 1,3- (or
1,4-) bis (isocyanatomethyl) cyclohexane (hydrogenated XDI), 2,2,4- (or2,4,4-) trimethylhexamethylene diisocyanate (TMDI)
Derived from one or a mixture of these monomers, for example, isocyanurate type polyisocyanates; burette type polyisocyanates; polyhydric alcohols such as 1,3-butanediol, trimethylolpropane, etc. A polyisocyanate-based curing agent represented by a urethane-type adduct and the like.

The isocyanate group of the polyisocyanate curing agent is blocked with a compound such as various oximes, caprolactams, phenols, imidazoles, hydroxypyridines, so-called active methylene compounds such as acetoacetic acid ester. Blocked isocyanate type curing agent.

For curing epoxy groups, for example polyfunctional amines, imidazoles, acid anhydrides. These curing agents (II) can be used by appropriately mixing them.

The blending ratio of the coating composition (I) of the present invention and the curing agent (II) as described above can be arbitrarily set according to the desired performance of the coating, but usually a melamine-based curing agent and In the case of an epoxy curing agent, the weight ratio of the main agent to the curing agent is in the range of 100/3 to 100/50, preferably 1
It is selected in the range of 00/5 to 100/40. Further, in the case of polyisocyanate and block isocyanate-based curing agents, the equivalent ratio of OH groups in the coating composition of the present invention to NCO groups in the curing agent is OH / NCO = 0.3 / 1 to 3 /
1, preferably in the range of 0.5 / 1 to 2.5 / 1.

In the coating composition, in addition to the above-mentioned main agent and curing agent, if necessary, solvents for adjusting viscosity, catalysts for promoting the curing reaction, pigments / dyes, light absorbers, and oxidation agents. It is possible to add stabilizers such as inhibitors and other additives for paints.

The coating composition thus obtained is compatible with various curing agents such as polyisocyanate, the pigment dispersibility, and the hardness of the cured coating film while maintaining the excellent weather resistance of the fluorine-based coating composition. The adhesiveness to the base material, the stain resistance of the coating film, etc. are significantly improved.

[0047]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the embodiments. The abbreviations used in the examples are listed below.

[Monomer] CTFE: Chlorotrifluoroethylene HBVE: 4-Hydroxybutyl vinyl ether IBVE: Isobutyl vinyl ether CHVE: Cyclohexyl vinyl ether DHF: 2,3-Dihydrofuran MMA: Methyl methacrylate CHMA: Cyclohexyl methacrylate HEMA: Methacryl Acid-2-hydroxyethyl TMPM: 4-methacryloyloxy-2,2,6
6-Tetramethylpiperidine HMPB: 2-hydroxy-4- (3-methacryloxy-2-hydroxypropoxy) benzophenone BMA: Butyl methacrylate FOEM: 2-perfluorooctylethyl methacrylate

[Polymerization Initiator] PBPV: t-Butylperoxypivalate AIBN: Azobisisobutyronitrile

[Molecular Weight] The molecular weight of the copolymer was determined from a polystyrene standard calibration curve using gel permeation chromatography.

[Apparatus used] -Device: Shimadzu LC-3A-Column: Tosoh Corporation TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL-Detector: Shimadzu RID-6A-Data processing: Shimadzu C-R4A ・ Carrier: Tetrahydrofuran

[Hydroxyl Value] The hydroxyl value is JIS K-00.
It measured according to 70.

[Paint Evaluation Method] 1. Blending and coating: "Duranate TPA" (manufactured by Asahi Kasei Co., Ltd.) as a curing agent was added to the resin solutions shown in the respective Examples and Comparative Examples so that NCO / OH = 1/1.
After blending in each, xylene was used as a thinner and adjusted with Ford cup # 4 for 15 seconds and then painted. 2. Pigment dispersibility: Each resin solution and various pigments are blended so as to have a predetermined pigment weight concentration, and dispersed for 2 hours using a sand mill, and the curing agent is blended as described in the above item 1 and coated, The gloss and the degree of pigment aggregation were visually evaluated.

3. Compatibility: The transparency of the clear coating film blended in the above item 1 was visually evaluated. 4. Coating film gloss: Measured according to JIS K-5400. 5. Contamination resistance: The paint film is contaminated with red magic ink, and
After standing at 0 ° C for 24 hours, petroleum benzine / ethanol = 5
It was wiped at 0/50 and the degree of contamination was judged. 6. Weather resistance: In accordance with ASTM G-53, an accelerated weather resistance test was conducted with a "QUV" test group of Q Panel Co., and 300
A gloss retention of 90% or more after 0 hour was regarded as acceptable.

[0055]

[Production Example-1] [Production of Resin (A)]: 7.7 g of potassium carbonate was charged into a stainless steel autoclave having an internal volume of 1 L, and after nitrogen substitution, the monomers, the initiator and the solvent shown in Table 1 were charged, and the mixture was heated to 67 ° C. Polymerization for 8 hours,
Resin A-1 and resin A-2 were obtained.

[0056]

[Production Example-2] [Production of Resin (B)]: A glass reactor having an internal volume of 1 L was purged with nitrogen, charged with the monomers, the initiator and the solvent shown in Table 2, and polymerized at 85 ° C. for 8 hours. Resin B-1, resin B-2 and resin B-3 were obtained.

[0057]

[Production Example-3] [Polymerization of Monomer Constituting Resin (A) in the Presence of Resin (B): A stainless steel autoclave having an internal volume of 1 L was charged with 7.7 g of potassium carbonate, and the atmosphere was replaced with nitrogen. Of (resin A-
After charging the constituent monomer of 1), an initiator and a solvent, and subsequently charging 142 g of a solution (resin B-1) (solid content 50% / xylene-butyl acetate), polymerization was carried out at 67 ° C. for 8 hours to obtain a resin. AB-1 was obtained.

[0058]

[Production Example-4] [Polymerization of Monomer Constituting Resin (B) in the Presence of Resin (A): A glass reactor having an internal volume of 1 L was purged with nitrogen, and then a (resin (A)) solution (solid 50% min / xylene) 80% solids
125 g of a concentrate of 100% was charged. Then, Table 2
After charging 150 g of the constituent monomer and the initiator of (Resin B-3) and heptane and polymerizing at 85 ° C. for 8 hours,
Add 25 g of n-butyl acetate and slowly cool to room temperature for Resin A
B-2 was obtained. The obtained liquid was a milky white stable dispersion liquid having a solid content of 50% and a particle size of polymer particles of 0.4 μm.

[0059]

[Production Example-5] [Production of Comparative Resin (C)]: A glass reactor having an internal volume of 1 l was purged with nitrogen, charged with the monomers, initiators and solvents shown in Table 2, and polymerized at 85 ° C for 8 hours. Then, a comparative resin C was obtained.

[0060]

Examples 1 to 7; Comparative Examples 1 and 2 Resin A, Resin B, Resin C blended in predetermined proportions, and Resin AB
-1, The coating performance of resin AB-2 was evaluated.
The results are shown in Table 3.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

As shown in Table 3, the resin according to the present invention is excellent in compatibility, pigment dispersibility and weather resistance. Further, the fluorine-based coating material of the present invention containing the fluorine-containing resin as a main component can give a coating film which is glossy and hard, and which has excellent adhesion to a substrate and excellent weather resistance under mild conditions. For example, it is useful as a baking paint for a colored rigid plate, a colored aluminum plate, an aluminum sash, or as a normally dry type paint that can be applied on site.

Further, regarding the material of the base material, in addition to metal materials, inorganic materials such as glass and concrete, FRP,
It is preferably used for coating plastics such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride and polyvinylidene chloride, and organic materials such as wood. Further, the fluorine-based paint is also useful in specific applications such as automobile top coats, exterior colored glass, and cement roof tiles.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C09D 133/00 PGF 7242-4J PGG 7242-4J 163/00 PJK 8416-4J PKE 8416-4J // C08F 2 / 44 MCS 7442-4J

Claims (5)

[Claims] 1. A number-average molecular weight of 500 containing fluorine in the molecule and having active hydrogen and / or an epoxy group.
To 50,000 resin (A) and an acrylic resin (B) having a number average molecular weight of 500 to 50,000 and having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule. As a component, and resin (A)
And a resin (B) in a weight ratio of 95: 5 to 5:95. 2. The coating resin according to claim 1, wherein the resin (B) also contains a fluoroalkyl group in the side chain. 3. In the presence of an acrylic resin having a number average molecular weight of 500 to 50,000, which has an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule, fluorine is contained in the molecule. And a method of producing a resin for coating material, which comprises polymerizing a monomer constituting a resin having active hydrogen and / or an epoxy group. 4. A number average molecular weight of 500 containing fluorine in the molecule and having active hydrogen and / or epoxy group.
Characterized by polymerizing a monomer constituting an acrylic resin having an ultraviolet absorption ability and / or an antioxidant ability and / or a radical scavenging ability in a molecule in the presence of a resin of 50,000 to 50,000, Manufacturing method of resin for paint. 5. A number average molecular weight of 500 containing fluorine in the molecule and having active hydrogen and / or epoxy group.
To 50,000 resin (A) and an acrylic resin (B) having a number average molecular weight of 500 to 50,000 and having an ultraviolet absorbing ability and / or an antioxidant ability and / or a radical scavenging ability in the molecule. As a component, and resin (A)
And a resin (B) in a weight ratio of 95: 5 to 5:95, the coating composition comprising the resin (I) for coating and a curing agent (II).